Sublimation thermal transfer printing sheet comprising novel magenta dyestuffs

ABSTRACT

Disclosed are magenta anthraquinone dyestuffs for sublimation thermaltransfer printing of one of the formulas ##STR1## wherein R is a halogen atom, methyl or methoxy; wherein R 1  is a hydrogen atom, hydroxyl, a halogen atom, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; and wherein R 2  is a hydrogen atom, a halogen atom, alkyl or 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, with the proviso that in formula (3) either R 1  or R 2  is not a hydrogen atom.

This is a continuation of application Ser. No. 07/550,745, filed Jul.10, 1990, now U.S. Pat. No. 5,168,092, which is a continuation-in-partof Ser. No. 07/291,896, filed Dec. 29, 1988, now abandoned.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention relates to magenta anthraquinone dyestuffs for usein sublimation thermaltransfer and to sublimation thermaltransfer sheetscomprising one or more thereof.

More specifically, the present invention relates to magentaanthraquinones having good adhesion and color development properties aswell as excellent fastness which can be used in a method for producingimages using a thermal head for heating and sublimation transferthereof. The anthraquinones of this application are characterized byhigh color density and excellent solubility when employed in sublimationthermaltransfer printing sheets, which printing sheets have hightransferring speed. In these respects, this invention surpasses theprior art.

The anthraquinones of the present invention are useful for producingcolored hard copies through a CRT color display, a color facsimile, amagnetic camera and the like utilizing a transfer type heat-sensitiverecording system as the means for recording information.

(2) Description of the Prior Art

Japanese Patent Laid-open Publication No. 78896/1984 discloses the useof compounds represented by the following general formula (A) as amagenta dyestuff for sublimation thermaltransfer: ##STR2##

wherein X is a hydrogen atom or methyl group, and R and R' each is amethyl group, ethyl group or straight-chain or branched propyl or butylgroup.

However, dyestuffs having the general formula (A) have poor light faderesistance and thus the preservation of information records employingthis dyestuff is defective.

In Japanese Patent Laid-open Publication No. 131293/1985, as magentadyestuffs for sublimation thermaltransfer there are disclosedanthraquinones which are represented by the following general formula(B): ##STR3## wherein X is an oxygen atom or sulfur atom, and A is astraight-chain or branched alkylene group, alkylene-O-alkylene group,alkylene-S-alkylene group, cyclohexylene group, phenylene group,##STR4##

However, undesirably a great deal of energy is required to transfer thisdyestuff and the cost of a machine which uses this dyestuff is thusuneconomically high.

Moreover, known 1-amino-2-phenoxy-4-hydroxyanthraquinone (CI. No. DispRed 60), 1-amino-2-phenylthio-4-hydroxyanthraquinone (Japanese PatentLaid-open Publication No. 159091/1985) and 1,4-diamino-2,3bisphenoxyanthraquinone (Japanese Patent Laid-open Publication No.268495/1986) are also used, but they have poor solubility in solventsemployed in an ink-based process, they have poor sublimation propertiesand are unsatisfactory with respect to dyestuff adhesion and fastnessproperties.

Moreover, these anthraquinone dyestuffs have a yellowish color andtherefore magenta dyestuffs in which absorption occurs in a longer wavelength range are in strong demand.

Japanese Patent Laid-open Publication No. 227093/1986 discloses ananthraquinone dyestuff, for heat-sensitive transfer recording,represented by the following general formula: ##STR5## wherein R is analkyl of 2 to 10 carbon atoms, an alkoxy of 2 to 10 carbon atoms, ortrifluoromethyl.

Japanese Patent Laid-open Publication No. 138559/1987 discloses ananthraquinone dyestuff represented by the following general formula:##STR6## wherein R is an alkyl such that the total molecular weight ofthe anthraquinone is more than 350.

However, recorded images on transfer sheets which comprise a dyestuffhaving the above general formulas (c) and (d) do not have satisfactorylight-fade resistance or color-fastness.

SUMMARY OF THE INVENTION

In a composition aspect, the present invention is directed to magentaanthraquinones dyestuffs useful for sublimation thermaltransferprocesses which are represented by one of the formulae ##STR7## whereinR is a halogen atom, methyl or methoxy; wherein R₁ is a hydrogen atom,hydroxyl, a halogen atom, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to4 carbon atoms; and wherein R₂ is a hydrogen atom, a halogen atom, alkylof 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, with theproviso that in formula (3) either R₁ or R₂ is not a hydrogen atom.

In another composition aspect, the present invention is directed tothermaltransfer sheets useful for thermal transfer processes whichemploy at least one magenta anthraquinone dyestuff of one of the aboveformulas, preferably which employ a mixture of at least one of formula(1) and at least one of formula (3).

In a process aspect, this invention relates to sublimationthermaltransfer processes employing an anthraquinone of this invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The magenta dyestuffs of this invention can easily be dissolved in asolvent, are excellent with respect to convertibility into ink,sublimation and fastness and are free from migration into andcontamination of the base material to which it is transferred bysublimation. The anthraquinones represented by formulas (1), (2) and (3)are described hereinbelow in accordance with preferred embodiments.

The alkyl groups of 1 to 4 carbon atoms, which can be straight-chain orbranched, include methyl, ethyl, n-propyl, isopropyl, n-butyl andisobutyl. The alkoxy groups of 1 to 4 carbon atoms can bestraight-chain, branched, secondary or tertiary and include methoxy,ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.

Halogen atoms include fluorine, chlorine, bromine and iodine.

R¹ and R² can be at the o-, m- or p-position.

The anthraquinones represented by the above formulas include1,4-diamino-2-phenoxyanthraquinones,1-amino-2-phenoxy-4-hydroxyanthraquinones and1,4-diamino-2,3-bisphenoxyanthraquinones.

In a preferred 1,4-diamino-2-phenoxyanthraquinone, R¹ is at them-position of the phenoxy group, which anthraquinones can be representedby the general formula (2): ##STR8## wherein R¹ has the values givenabove.

The 1,4-diamino-2-phenoxyanthraquinones represented by the generalformula (2) have a magenta color and in sublimation thermaltransferprocesses using these compounds, the amount thereof to be transferredcan be regulated by altering the energy which is fed to theheat-transfer head, so that gradation recordings can easily be produced.Therefore, these magenta anthraquinones are suitable for full colorrecords. In particular, those in which the m-position of the phenoxygroup bears a substituent exhibit superior performance characteristicscompared to conventional ones.

Preferred examples of R¹ in the compounds represented by formula (2)include alkyl groups such as methyl, ethyl, n-propyl, isopropyl andn-butyl; alkoxy groups such as methoxy, ethoxy, n-propoxy and n-butoxy;hydroxyl; and halogen atoms such as fluorine, chlorine and bromine.

Other preferred 1-amino-2-phenoxy-4-hydroxyanthraquinones are thosewherein R¹ is at the m-position of the phenoxy group, viz. compoundsrepresented by the general formula (1): ##STR9## wherein R is as definedabove, except a hydrogen atom.

These compounds which have R at the m-position have better solubility insolvents employed for ink formation, which is the essential requirementof the transfer dyestuff, than the corresponding position isomers inwhich R is the o- or p-position.

Additionally, when thermally transferred, the amount thereof to betransferred can be regulated by altering the energy which is fed to theheat-transfer head, so that gradation recordings can easily be produced.Therefore, these magenta anthraquinones are suitable for full colorrecords.

Preferred examples of R¹ in the compounds represented by formula (IV)include methyl, methoxy and halogen atoms, such as fluorine, chlorine,bromine and iodine.

The 1,4-diamino-2,3-bisphenoxyanthraquinones which are another group ofpreferred anthraquinones of this invention are compounds represented bythe general formula (3): ##STR10##

When thermally transferred, the amount of these1,4-diamino-2,3-bisphenoxyanthraquinones to be transferred can beregulated by altering the energy which is fed to the heat transfer head,so that halftone printings can easily be produced. Therefore, thesecompounds are suitable for full color records.

The compounds of formula (3) have particularly good solubility inorganic solvents and dispersibility in water, above all, one in which R¹and R² lie at m-position is better from the view point of solubility insolvents employed for ink formation. Therefore highly concentrated inksin which the dyestuff is uniformly dissolved or dispersed can easily beproduced. Consequently, images having good color density can berecorded.

In the compounds of formula (3), the two phenoxy groups can be identicalor different but, as noted above, both R¹ and R² are not hydrogen atomssimultaneously.

The anthraquinones represented by the formulas (1), (2) and (3) of thepresent invention generally have the following common characteristics:

They are stable to heat, light, moisture and chemicals and thus are notthermally decomposed during transfer recording and the recorded imagesproduced therefrom have excellent stability.

The compounds have good solubility in organic solvents and gooddispersibility in water and highly concentrated ink in which thedyestuff is uniformly dissolved and dispersed can easily be produced.Consequently, images having good color density can be recorded. Thus,these compounds are commercially valuable.

The anthraquinones represented by formulas (1), (2) and (3) can besynthesized by reacting a compound represented by the general formula(I): ##STR11## wherein X² is a chlorine atom or NaSO₃, X³ is a hydrogenatom or chlorine atom, and X⁴ is a hydroxyl group or NH₂ with a compoundrepresented by the general formula (II): ##STR12## wherein R⁵ is ahydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of1 to 4 carbon atoms, a hydroxyl group or a halogen atom, in an aproticpolar solvent.

The 1,4-diamino-2-phenoxyanthraquinones represented by the generalformula (2) can be synthesized by reacting a compound of the generalformula (I) in which X² is a chlorine atom or NaSO₃, X⁴ is NH₂ and X³ isa hydrogen atom, i.e., 1,4-diamino-2-chloroanthraquinone or1,4-diaminoanthraquinone-2-sodium sulfonate, with a substituted phenolrepresented by the formula ##STR13## wherein R¹ is the same as in thegeneral formula (2), in a polar organic solvent such as sulfolane and inthe presence of a base.

The 1-amino-2-phenoxy-4-hydroxyanthraquinones represented by the generalformula (1) can be synthesized by thermally reacting a compoundrepresented by the formula (I) in which X² is a chlorine atom, X³ is ahydrogen atom, and X⁴ is a hydroxyl group, i.e.,1-amino-2-chloro-4-hydroxyanthraquinone, of the formula ##STR14## with aphenol represented by the formula ##STR15## wherein R¹ is the same asdefined in the general formula (1) except a hydrogen atom, in an aproticpolar solvent in the presence of a base.

The 1,4-diamino-2,3-bisphenoxyanthraquinone dyestuff can be synthesizedas follows:

When R¹ and R² in formula (3) are different from each other, there areused compounds represented by the general formulae (III) and (IV):##STR16## wherein R¹ and R² have the same values in the general formula(3) and are different from each other.

First, the compound represented by the formula (I) in which each of X²and X³ is a chlorine atom, and X⁴ is NH₂, i.e.,1,4-diamino-2,3-dichloroanthraquinone, is reacted with a molarequivalent amount of a compound of formula (III), in an aprotic polarsolvent, e.g., at a temperature of 140° to 160° C., to produce acompound represented by the general formula (V): ##STR17## wherein R¹ isthe same as in the general formula (I), and then isolating the thusproduced compound, which is thermally reacted with a compound of formula(IV) in an aprotic polar solvent, e.g., at a temperature of 160° to 180°C., to obtain the desired anthraquinone represented by the generalformula (3).

When R¹ and R² in formula (3) are identical, the compound represented byformula (I) in which each of X² and X³ is a chlorine atom, and X⁴ is NH₂i.e., 1,4-diamino-2,3-dichloroanthraquinone is reacted with a compoundof formula (II) in an aprotic polar solvent, e.g., at a temperature of160° to 180° C., to produce the desired1,4-diamino-2,3-bisphenoxyanthraquinone.

Procedures to heat transfer printing of synthetic materials aredisclosed in French Patent Nos. 1213330 and 1585119 and in German PatentNo. 1769757, and dystuffs, regulators and auxiliary carriers used insuch procedures are disclosed in German Laid-open Patent ApplicationNos. 1771813 and 171812, all of whose disclosures are incorporatedherein by reference.

An ink for thermaltransfer record from an anthraquinone of generalformula (1), (2) or (3) can be prepared by mixing the dyestuff with asuitable resin, solvent and the like. Furthermore, the thermaltransfermay be accomplished by first applying the thus obtained ink onto asuitable transfer substrate to form a transfer sheet and then applyingthis sheet onto the face of the printable substrate onto which an imageis to be recorded, and heating and pressing the resulting laminate fromthe back surface of the transfer sheet by means of a heat-transferrecording head.

The resin used for the preparation of the ink can be one which is usedfor the manufacture of conventional printing inks, examples of whichinclude oil resins such as rosin, phenolic resin, xylene resin,petroleum resin, vinyl resin, polyamide, alkyd resin, nitrocellulose andalkylcellulose; and aqueous resins such as maleic resin, acrylic resin,casein resin, shellac and glue.

Examples of the solvent which can be used for the preparation of the inkinclude alcohols such as methanol, ethanol, propanol and butanol;cellosolves such as methyl cellosolve and ethyl cellosolve; aromaticssuch as benzene, toluene and xylene; esters such as ethyl acetate andbutyl acetate; ketones such as acetone, methyl ethyl ketone andcyclohexanone; hydrocarbons such as ligroin, cyclohexane and kerosene;and dimethylformamide. If an aqueous resin is selected, water or amixture of water and one of the above-mentioned water-miscible solventscan be used.

Suitable examples of transfer substrates onto which the ink is appliedinclude thin papers such as condenser paper and glassine paper; andfilms of plastics having good heat resistance, such as polyester,polyamide and polyimide. The thickness of the transfer substratepreferably is in the range of 5 to 50 μm so as to increase the heattransfer efficiency from the heat-transfer recording head to thedyestuff.

Examples of the printable materials onto which images can be recordedinclude fibers, fabrics, films, sheets and molded articles made frompolyolefin resins, such as polyethylene and polypropylene; halogenatedpolymers such as polyvinyl chloride and polyvinylidene chloride; vinylpolymers such as polyvinyl alcohol, polyvinyl acetate and polyacrylicesters; polyester resins, such as polyethylene terephthalate andpolybutylene terephthalate; polystyrene resins; polyamide resins;copolymer resins of olefins, such as ethylene and propylene and othervinyl monomers; ionomers; cellulosic resins, such as cellulose diacetateand cellulose triacetate; polycarbonates; polysulfones; polyamides andthe like.

Particularly preferred as substrates are fabrics, sheets and films madefrom polyethylene terephthalate.

Additionally, there can be employed the usual papers employed in thermalprinting, e.g., cellulosic papers coated or impregnated with theabove-mentioned resins containing acidic fine particles such as silicagel, laminates of resin films, and specially processed papers which havebeen subjected to an acetylation treatment. When these special papersare used as the printable substrate, good images can be recorded thereonwhich are excellent in image stability at a high temperature and a highhumidity. Moreover, synthetic papers made from various resins can bealso used.

After transfer recording the printed surface can be covered with a clearcoating. For example, a polyester film can be laminated onto the surfacebearing the transferred and recorded image by heat pressing, whereby thecolor development of the dyestuff and the storage stability of recordedimage can be improved.

The performance of the dyestuffs represented by the general formulas(1), (2) and (3) will be described in detail in accordance with exampleswhich follow, in which examples, "part" and "parts" are based on weight.cl EXAMPLE 1

(i) Preparation of Ink

    ______________________________________                                        1,4-Diamino-2(3-methylphenoxy)                                                                        3      parts                                          anthraquinone                                                                 Polybutyral resin       4.5    parts                                          Methyl ethyl ketone     46.25  parts                                          Toluene                 14.0   parts                                          ______________________________________                                    

To prepare an ink, the mixture of the above-mentioned composition wasblended by mixing with glass beads for about 30 minutes by means of apaint conditioner.

(ii) Preparation of Transfer Sheet

The thus prepared ink was applied in a conventional manner onto a 9 μmpolyethylene terephthalate film, the back surface of which had beensubjected to a heat resistance treatment by the use of a gravurecalibrater (plate depth=30 μm). The ink was applied at a dry weight rateof about 1.0 g/m². Afterward, the applied ink was dried by heating thefilm.

(iii) Preparation of Material to be Recorded

    ______________________________________                                        Polyester Resin (Vylon 103;                                                                           0.8    part                                           Toyobo Co., Ltd.; Tg = 47° C.)                                         EVA Polymeric Plasticizer                                                                             0.2    part                                           (Erbaloy 741p; Mitsui Polychemical                                            Co., Ltd.; Tg = -37° C.)                                               Amino-modified Silicone 0.04   part                                           (KF 857; The Shin-Etsu Chemical                                               Co., Ltd.)                                                                    Epoxy-modified Silicone 0.04   part                                           (KF-103; The Shin-Etsu Chemical                                               Co., Ltd.)                                                                    Methyl Ethyl Ketone/Toluene/                                                                          9.0    parts                                          Cyclohexane (weight ratio =                                                   4:4:2)                                                                        ______________________________________                                    

These components were mixed conventionally in order to prepare a coatingsolution, which was then applied onto a face of a synthetic paper suchas polyethylene or polyester using a bar coater (RK Print CoatInstruments Co., Ltd.; No. 1) at a dry weight rate of about 4.5 g/m²,followed by drying at 100° C. for 15 minutes.

(iv) Transfer Recording

The ink-bearing free of the transfer sheet was placed against the coatedface of the thus-produced synthetic paper so that the inked surface ofthe former was in intimate contact with the coated surface of the latterand recording was then achieved by heating and pressing the resultinglaminate from the back surface of the transfer sheet by a heat-transferrecording head under conditions of a voltage=10 V and a printing time of4.0 milliseconds, whereby an image having a magenta color and a colordensity of 1.9 was recorded.

The color density was measured by the use of a densitometer, modelRD-514 (filter=Latten No. 58) made by U.S. Macbeth Co., Ltd. and wascalculated in accordance with the following formula:

Color Density=log₁₀ (Io/I)

Io=Intensity of reflected light from a standard white reflective plate

I=Intensity of reflected light from a specimen.

For the recorded image, a light resistance test was carried out by theuse of a xenon fade meter (Suga Testing Machine Co., Ltd.) at a blackpanel temperature of 63±2° C. and 90% relative humidity. This testconfirmed that the recorded image was scarcely discolored by theirradiation for 40 hours and was excellent in stability at hightemperatures and high humidity.

The color fastness of the recorded image was evaluated by allowing thespecimen to stand at 50° C. for 48 hours, and then observing thevividness of the image and the colored state of the white paper afterthe surface of the specimen had been rubbed against a white paper.According to this test, the vividness of the image was unchanged and thewhite paper against which the image surface had been rubbed was notcolored, which indicated that the fastness of the recorded image wasgood.

In the following examples and comparative examples, the preparation ofinks, transfer sheets and materials to be recorded as well as thetransfer recording were carried out in accordance with the sameprocedure as in Example 1. The resulting of color densities are setforth in Table 1.

EXAMPLE 2

1,4-Diamino-2(3-methoxyphenoxy)anthraquinone was used as the dyestuffand a magenta color image having a color density of 1.9 was recorded.

In the color fastness test, the vividness of the recorded image wasunchanged and a white paper against which the surface of the image hadbeen rubbed was not colored. In addition, color fastness was good.

EXAMPLE 3

1,4-Diamino-2(3-chlorophenoxy)anthraquinone was used as the dyestuff anda magenta color image having a color density of 2.0 was recorded.

In the color fastness test, the vividness of the recorded image wasunchanged and a white paper against which the surface of the image hadbeen rubbed was not colored. In addition, color fastness was good.

EXAMPLE 4

1,4-Diamino-2(3-hydroxyphenoxy)anthraquinone was used as the dyestuffand a magenta color image having a color density of 1.9 was recorded.

In the color fastness test, the vividness of the recorded image wasunchanged and a white paper against which the surface of the image hadbeen rubbed was not colored. In addition, color fastness was good.

EXAMPLE 5

1-Amino-2(3-methylphenoxy)-4-hydroxylanthraquinone was used as thedyestuff and a magenta color image having a color density of 1.9 wasrecorded.

The stability of the image at a high temperature and a high humidity wasexcellent. In the color fastness test, the vividness of the recordedimage was unchanged and a white paper against which the surface of theimage had been rubbed was not colored. In addition, color fastness wasgood.

EXAMPLES 6, 7 and 9 to 14

In these examples the respective dyestuffs shown in Table 1 were usedand vivid magenta color images having color densities shown in Table 1were transferred and recorded.

Furthermore, the light resistance and fastness of the recorded imageswere good, as in Example 1.

EXAMPLE 8

1,4-Diamino-2,3-bis(3-methylphenoxy)anthraquinone was used as thedyestuff and a magenta color image having a color density of 1.8 wasrecorded.

The stability of the image at a high temperature and a high humidity wasexcellent. In the color fastness test, the vividness of the recordedimage was unchanged and a white paper against which the surface of theimage had been rubbed was not colored. In addition, fastness was good.

COMPARATIVE EXAMPLE 1

1,4-Diamino-2(2-hydroxyphenoxy)anthraquinone was used as the dyestuffand a magenta color image having a color density of only 0.61 wasrecorded. In the color fastness test, the vividness of the recordedimage was poor and a white paper against which the surface of the imagehad been rubbed was colored.

COMPARATIVE EXAMPLE 2

1,4-Diamino-2(4-hydroxyphenoxy)anthraquinone was used as the dyestuffand a magenta color image having a color density of only 0.54 wasrecorded. Moreover, in the color fastness test, the vividness of therecorded image was poor and a white paper against which the surface ofthe image had been rubbed was colored.

COMPARATIVE EXAMPLE 3

1-Amino-2-phenoxy-4-hydroxyanthraquinone was used as the dyestuff toprepare an ink. However, the dyestuff did not dissolve acceptably in thesolvent and a part of the dyestuff remained undissolved in the form ofcoarse crystals.

Material to be recorded, application of the ink to a transfer sheet anddrying were then carried out as described above. The transfer sheetproduced therefrom was not uniform and coarse grains were depositedthereon.

Transfer recording was performed using the transfer sheet. A non-uniformimage was transferred and recorded and overall the quality of the imagewas poor.

COMPARATIVE EXAMPLES 4 and 5

1-Amino-2(2-methylphenoxy)-4-hydroxyanthraquinone and1-amino-2(4-methoxyphenoxy)-4-hydroxyanthraquinone were used asdyestuffs to prepare thermal inks. Materials to be recorded were thenprepared, followed by applying the ink to the transfer sheet, drying andtransfer recording, all as in Comparative Example 3. The resultsobtained with the respective dyestuffs were similar to those ofComparative Example 3 and the overall quality of the images was poor.

                                      TABLE 1                                     __________________________________________________________________________           Dyestuff                   Color Density                               __________________________________________________________________________    Example 1                                                                            1,4-Diamino-2(3-methylphenoxy)anthraquinone                                                              1.9                                         Example 2                                                                            1,4-Diamino-2(3-methoxyphenoxy)anthraquinone                                                             1.9                                         Example 3                                                                            1,4-Diamino-2(3-chlorophenoxy)anthraquinone                                                              2.0                                         Example 4                                                                            1,4-Diamino-2(3-hydroxyphenoxy)anthraquinone                                                             1.9                                         Example 5                                                                            1-Amino-2(3-methylphenoxy)-4-hydroxyanthraquinone                                                        1.9                                         Example 6                                                                            1-Amino-2(3-methoxyphenoxy)-4-hydroxyanthraquinone                                                       1.8                                         Example 7                                                                            1-Amino-2(3-chlorophenoxy)-4-hydroxyanthraquinone                                                        1.6                                         Example 8                                                                            1,4-Diamino-2,3bis(3-methylphenoxy)anthraquinone                                                         1.8                                         Example 9                                                                            1,4-Diamino-2,3bis(2-methylphenoxy)anthraquinone                                                         1.7                                         Example 10                                                                           1,4-Diamino-2,3bis(3-methoxyphenoxy)anthraquinone                                                        1.6                                         Example 11                                                                           1,4-Diamino-2,3bis(4-tert-butylphenoxy)anthraquinone                                                     1.4                                         Example 12                                                                           1,4-Diamino-2-phenoxy-3(3-methylphenoxy)anthraquinone                                                    1.5                                         Example 13                                                                           1,4-Diamino-2,3bis(3-chlorophenoxy)anthraquinone                                                         1.4                                         Example 14                                                                           1,4-Diamino-2,3bis(4-methylphenoxy)anthraquinone                                                         1.7                                         Comp. Ex. 1                                                                          1,4-Diamino-2(2-hydroxyphenoxy)anthraquinone                                                             0.61                                        Comp. Ex. 2                                                                          1,4-Diamino-2(4-hydroxyphenoxy)anthraquinone                                                             0.54                                        Comp. Ex. 3                                                                          1-Amino-2-phenoxy-4-hydroxyanthraquinone                                                                 1.2                                         Comp. Ex. 4                                                                          1-Amino-2(2-methylphenoxy)-4-hydroxyanthraquinone                                                        1.0                                         Comp. Ex. 5                                                                          1-Amino-2(4-methoxyphenoxy)-4-hydroxyanthraquinone                                                       0.8                                         __________________________________________________________________________

In the following examples, transfer sheets, materials to be recorded andthe transfer recording were carried out in accordance with the procedureof Example 1.

EXAMPLES 15-18 ##STR18##

Tests were conducted for each ratio of the anthraquinone of formula (3a)to formula (1a) indicated in table 1 using inks comprising the followingproportions (weight basis):

    ______________________________________                                        Anthraquinones of formulas (3a) and (1a)                                                               3.0    parts                                         Polybutyral resin        4.5    parts                                         Methyl ethyl ketone      46.25  parts                                         Toluene                  46.25  parts                                         ______________________________________                                    

To prepare an ink, a mixture of the above composition was blended bymixing with glass beads for about 30 minutes by means of a paintconditioner.

Evaluations for light-fade resistance and color fastness were done inthe same manner as in Example 1 in the original specification.

As a result, the tests in all cases confirmed that the recorded imageshaving a magenta color were scarcely discolored and had excellentstability at high temperatures and high humidity, and that the colorfastness of the recorded images was good. The vividness of the imageswas unchanged and the white paper against which the image surfaces wasrubbed was not colored.

The resulting color densities are set forth in Table 1.

                  TABLE 1                                                         ______________________________________                                                       Ratio of (3a) to (1a)                                          Example       (3a):(1a)      Color Density                                    ______________________________________                                        15       0.9        2.1      2.10                                             16       1.2        2.8      2.00                                             17       1.2        2.8      2.40                                             18       1.6        2.4      2.30                                             ______________________________________                                    

EXAMPLES 19-31

In these examples, the anthraquinones represented by general formulas(3) and (1) were used. The same tests were conducted using inks of thesame composition except for the anthraquinones indicated in Table 2.

As a result, the tests confirmed that the light resistance and colorfastness of the recorded images having a magenta color were good in allcases as in Example 1. The resulting color densities are shown in Table2.

Although the invention has been described with preferred embodiments, itis to be understood that variations and modifications may be resorted toas will be apparent to those skilled in the art. Such variations andmodifications are to be considered within the purview and the scope ofthe claims appended hereto.

                  TABLE 2                                                         ______________________________________                                        Formula (3)           Formula (1)                                                                              Color                                        Example                                                                              R.sub.1  R.sub.2    Parts                                                                              R     Parts                                                                              density                            ______________________________________                                        19     m-CH.sub.3                                                                             p-C.sub.2 H.sub.5                                                                        0.9  CH.sub.3                                                                            2.1  1.80                               20     m-CH.sub.3                                                                             p-Cl       0.9  CH.sub.3                                                                            2.1  1.75                               21     m-CH.sub.3                                                                             m-Cl        1.05                                                                              CH.sub.3                                                                             1.95                                                                              1.75                               22     m-CH.sub.3                                                                             o-Cl       1.2  CH.sub.3                                                                            1.8  1.74                               23     m-CH.sub.3                                                                             p-OCH.sub.3                                                                              0.9  CH.sub.3                                                                            2.1  1.75                               24     m-CH.sub.3                                                                             m-OCH.sub.3                                                                              1.2  CH.sub.3                                                                            1.8  1.75                               25     p-CH.sub.3                                                                             m-C.sub.2 H.sub.5                                                                         1.05                                                                              CH.sub.3                                                                             1.95                                                                              1.82                               26     p-CH.sub.3                                                                             p-C.sub.2 H.sub.5                                                                        0.9  CH.sub.3                                                                            2.1  1.78                               27     p-CH.sub.3                                                                             p-C.sub.2 H.sub.5                                                                        1.2  Cl    1.8  1.75                               28     m-CH.sub.3                                                                             H           1.05                                                                              Cl     1.95                                                                              1.76                               29     m-CH.sub.3                                                                             H          1.2  OCH.sub.3                                                                           1.8  1.73                               30     OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         0.9  OCH.sub.3                                                                           2.1  1.70                               31     H                                                                                       ##STR19## 1.2  CH.sub.3                                                                            1.8  1.65                               ______________________________________                                    

What is claimed is:
 1. A sublimation thermaltransfer printing sheetcomprising a substrate having applied thereto an ink comprising adyestuff, a binder resin and a solvent, wherein said dyestuff comprisesa compound of one of the formulas: ##STR20## wherein R is a halogenatom, methyl or methoxy; wherein R₁ is a hydrogen atom, hydroxyl, ahalogen atom, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbonatoms; and wherein R₂ is a hydrogen atom, a halogen atom, alkyl of 1 to4 carbon atoms or alkoxy of 1 to 4 carbon atoms, with the proviso thatin formula (3) either R₁ or R₂ is not a hydrogen atom.
 2. Athermaltransfer printing sheet of claim 1 comprising a compound offormula (1).
 3. A thermaltransfer printing sheet of claim 1 comprising acompound of formula 1 wherein R is a chlorine atom.